KALINGA INSTITUTE OF INDUSTRIAL TECHNOLOGY (KIIT)

(Deemed to be University)
School of Applied Sciences (Chemistry)
Subject Code-CH1007
Chapter-1
Thermodynamics & Equilibrium

Lecture-1: Introduction, Concept of internal energy, enthalpy and entropy

Thermodynamics (thermochemistry)-is the study of energy flow during a chemical reaction.

Thermodynamics was developed to know the most efficient way of converting heat into work!

Thermodynamics allows you to predict whether or not a reaction will occur (feasibility).
Thermodynamics can predict spontaneity of a reaction but says nothing about the rate of a
reaction.

The System and the Surroundings; A system in thermodynamics refers to that part in which
observations in thermodynamic changes are made and remaining part of universe constitutes the
surroundings.

There are seven important thermodynamic parameters (state functions): P (pressure), V

(volume), T (temperature), H (enthalpy), S (entropy), U (internal energy) and G (Gibbs free
energy)

A Thermodynamic process is when a system undergoes a series of changes.

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Properties of the Thermodynamics System:
Extensive property (depend on system mass) Intensive property (independ on system mass)
Volume, Number of moles, Mass, Internal Refractive index, Surface tension, density,
energy, enthalpy, entropy, free energy, heat temperature, Boiling point, Freezing point,
capacity molar volume
Dividing the system in half does not change the value of an intensive property.

How do we determine the energy changes in a thermodynamic process? (Work and Energy)
(a) Work (w)-Path function, (J/kJ), j/mol or kJ/mol if expressed for 1 mol
�= − ��� �� .................

Here, dV=(Vf-Vi)= (-) ve. Hence w= (+) ve. Work is performed on the system.
Work done by system w is (- ve), work performed on the system w is (+ ve)

(b) Heat (Q)-Path function, (J/kJ), j/mol or kJ/mol if expressed for 1 mol
Form of energy change when there is temperature difference. Can be calculate from heat
capacity of a material �� = ���
Heat capacity (C), Cv and Cp, CP-Cv=R

(c) Enthalpy (H)- State function, (J/kJ), j/mol or kJ/mol if expressed for 1 mol
Heat content of a system or a substance. � = � + ��
2
�� = (��)� , Heat absorbed/desorbed by the system at constant pressure P is change in
enthalpy.
�� = ��� ��

(d) Internal energy (U)- State function, (J/kJ), Total energy of the system.
Change in internal energy can be measured, not the internal energy.
�� = (��)� . Heat absorbed/desorbed by the system at constant volume V is change in internal
energy.
�� = ��� ��

(e) Entropy (S)- State function, (J/kJ), randomness in a system, measure of spontaneity of a
system. Change in entropy can be measured, not the entropy.
��
����� =
�
For reversible process, ∆������� + ∆������������ = 0
For irreversible process, ∆������� + ∆������������ > 0

Review Question-
1 What will be internal energy change of a system if q amount of heat is taken out from a system and no
work is performed? What kind of system it can be?
2 What will be internal energy change of a system if q amount of heat is supplied and w amount of work
is performed by it?
3 2 litres of an ideal gas expands isothermally to 10 litres against vacuum, how much heat is absorbed
and how much work is done in the expansion?
4 2 litres of an ideal gas expands isothermally to 10 litres against 1 atm external pressure, how much heat
is absorbed and how much work is done in the expansion?
5 Calculate the change in internal energy and enthalpy when 32 g of O2 is heated from O C to 100 C.
6 1.3×108 J of energy was added to a cylinder with a moving piston. The volume changed from 4.0×106 L
to 4.5×106 L against an external pressure of 1atm. Calculate the internal energy change.
7 1500 J of heat is added to the gas and the gas does not work and no work is done on the gas. The
internal energy (ΔU) change and temperature change (ΔT) for the processes involving 1 mole of an
ideal mono atomic gas will be
8 5000J of energy was added to 2 mole of mono atomic ideal gas enclosed in a cylinder with a moving
piston at 500K. The gas performs 7500J of work. What is the final temperature of the system?

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 9 In a thermodynamic process volume of gas expanded from 200ml to 2000ml against a constant
pressure of 745torr. During the process, 20 calories of heat energy was released to the surroundings.
What was the internal energy change for the system in joules? (1 L atm = 101.3 J, 1atm=760 torr)
10 Heat of combustion of methane is measured in a bomb calorimeter at 300K and is found to be -
900kJ/mol.

What is enthalpy change?

11. 1kg of H2O (l) is heated from 30 °C to 50 °C at 1 bar pressure. Calculate change in entropy. (Cp=75.3 J/mol
K).

Lecture-2: Entropy calculations involving ideal gases (expansion, mixing etc.)

��
�� =
�
From 1st law of thermodynamics- �� = �� − ���
Then,
�� + ���
∆� =
�
and applying dU=nCvdT, solution leads to

�2 �
∆� = ��� �� �1
+ �� ln �2 for (T, V) variable
1

�2 �1
∆� = ��� ��
�1
+ �� ln
�2
��� (T, P) variable

Entropy of mixing (ΔS)mix-

��
∆� = ���� � (at constant T and P).
�

(∆�)��� = ∆�� + ∆��

�� +�� �� +��
∆�� = �� ���
��
and ∆�� = �� ��� ��

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 (∆�)��� =− �� �� ����

χi is mole fraction, and

��
�� =
��
(n is mole number)

Review Question-
1. Show that entropy of mixing is maximum when χ1 = χ2= 0.5.
2. 2 mol of mono-atomic gas expand from a state (25 °C, 1atm) to another (50 °C, 0.5atm). Calculate ΔS.
3. 1 mol of H2 and 9 mol of N2 are mixed at 298K and 1 atm pressure. Calculate the entropy change
(assuming both the gasses behave ideally in this thermodynamic conditions).
4. Calculate the change in entropy for one mole of an ideal gas when its temperature rises from 300 K to 600
K under (i) isochoric and (ii) Isobaric condition. Given: Cv = 2.5 R)
5. What would be entropy change when 10 moles of an ideal gas be doubled in volume isothermally? [ ∆S =
57.63 jK-1]
6. Enthalpy of vaporization for CCl4 is 43.0 kJ/mol at boiling point 76.7 °C. If 1 mol is vaporized, calculate
the entropy change.

Lecture-3: Concept of free energy (A and G), Gibb’s-Helmholtz equation, conditions of

spontaneity and equilibrium
Free energy is the available energy in a system in a given set of thermodynamic conditions that
can be extracted to perform work.
(a) Helmholtz work function (A)- The useful work obtainable from a closed
thermodynamic system at a constant temperature and volume.
� = �(�, �)
� = � − ��
(b) Gibb’s free energy (G)- It is the energy available to do non-PV work in a
thermodynamically-closed system at constant pressure and temperature.
� = � �, �
� = � − ��
�
� = �0 + ������ ∆� = ����� �2
1

(c) Gibb’s Helmholtz relation-

�(∆�)
∆� = ∆� + �
�� �
Review Question-

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 1 Derive �� = ��� − ���, �� = �� + ���
2 5mol of ideal gas expand isothermally from 1l to 10l at 27 °C. Calculate change in free energy.
3 When one mole Glucose is oxidised to carbon dioxide and water at 298 K, calorimetric measurements
given ∆U0r = -2808 kJ/mol and ∆Sr = 182.4 jK-1mol-1. How much of this energy change can be
extracted as (a) heat at constant pressure, ∆Hr , (b) work.
4 The reaction N2 (g) + 3H2 (g) → 2NH3 (g) was carried out in a pressure vessel at 101.3 kPa and
300K.The value of ΔG - ΔA is
5 Calculate standard free energy change for
�2 (�) + 3�2 (�) → 2��3 (�) at 25 °C.
ΔH° formation is -45.9 kJ/mol for NH3. S° for N2, H2 and NH3 is 191.5 J/K, 130.6 J/K and 193 J/K
respectively.

Lecture-4: Derivation and applications of van’t Hoff isotherm and isochore

van’t Hoff equations-
� = �0 + �����
So, for a reversible reaction �� + �� ⇌ �� + ��
∆� = ∆�0 + ������
At equllibrium, ΔG is zero.
van’t Hoff isotherm ∆�0 =− �������
∆�0 ∆�0
van’t Hoff isochore ����� =− ��
+ �

Exothermic reaction vs endothermic reaction.

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 ��1 ∆�0 1 1
�� = ( − )
��2 � �1 �2
Review Question-
1 For the reaction �2 + 3�2 ⇌ 2��3 , Kp is 4.34×10-3 at 300K. Estimate Kp at 600K.
2 Kp for a reaction 1.6 x 10-4 atm-2 at 4000 C. what will be the Kp at 5000C ? Heat of reaction in this
temperature range is -25 kcal
3 Calculate the equilibrium constant for the following reaction at 400 K.
2 NOCl (g) ⇌ 2 NO (g) + Cl2 (g)
Given: ∆H0 = 80 kj mol-1, ∆S0 120 jK-1mol-1
� ∆� ∆�
4. Prove that �� �
=−
�2
�

5. If ΔG° for the reaction;

2��3 � + ��2 � → ��2 ����2 � + �2 � �
is 13.6kJ/mol at 25 °C. Calculate equilibrium constant
Lecture-5: Derivation and applications of Clapeyron-Clausius equation
Pressure and Temperature relation for equilibrium condition between two phase
I. Single component system
II. Two phase are in equilibrium such as
�2 �(�) ⇌ �2 �(�) Vaporization �2 �(�) ⇌ �2 �(�) Sublimation

�2 ∆� �2 − �1
�� =
�1 � �1 �2
ΔHvap (liq⇌gas) and ΔHsub (solid⇌Vap)

Review Question-
1. Benzene boiling point at atmospheric pressure is 80.1 °C. At what temperature it will evaporate if the
pressure drops to 260 mmHg. Ginen ΔHvap=30.72 kJ/mol.
2. At what temperature will water boil when the atmospheric pressure is 600 mm of Hg? Given latent heat of
vaporisation is 545.5 cal g-1 .
3. The vapour pressure of water at 950 C is 634 mm of Hg. What will be the vapour pressure at 1500 C?
Given ∆H = 41.27 kj mol-1.
4. Calculate the molar heat of vaporisation (ΔHvap) of ether between 330 C and 34 0 C. Given: vapour pressure
of ether at 330 C and 34 0 C are 750 mm of Hg and 760 mm of Hg, respectively.
5. Calculate the vapour pressure of an organic solvent having boiling point of 325 K. the vapour pressure for
solvent is 0.3222 atm at 305 K.
6. The heat of vaporization of benzene is 7.413 kcal/mol at 80 °C. What is the vapor pressure at 27 °C.?

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Lecture-6: Partial molar properties, concept of chemical potential, Gibb’s -Duhem equation &
application
Partial molar properties; Chemical potential
The partial molar free energy is equal to the chemical potential. In words, the partial molar free
energy is the change in total free energy that occurs per mole of component i added, with all
other components constant (at constant T, P and other component amounts).
∂Gi
μi = ( )T,P,1,2,3………………………..…i−1
∂ni
�� = �0 + ������

G=f(T, P, n1, n2.......ni)

�� = �� ���

�� ��� = 0................................................Gibb’s Duhem equation.

Review Question-
1. Prove that chemical potentials of both the component are interdependent in a binary component system.
2. Find the change in chemical potential of ethanol at 300 K upon addition of a solute assuming ideal
behaviour. Given that the mole fraction of the solute is 0.02.
3. Find the change in chemical potential of a substance if the partial pressure of an ideal gas changes from
0.25 atm to 1 atm.
4. Explain partial molar property. It is an extensive or intensive property?